WO2005058989A1 - Copolymeres a base de tert.-butyl(meth)acrylate et leur utilisation - Google Patents

Copolymeres a base de tert.-butyl(meth)acrylate et leur utilisation Download PDF

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Publication number
WO2005058989A1
WO2005058989A1 PCT/EP2004/013984 EP2004013984W WO2005058989A1 WO 2005058989 A1 WO2005058989 A1 WO 2005058989A1 EP 2004013984 W EP2004013984 W EP 2004013984W WO 2005058989 A1 WO2005058989 A1 WO 2005058989A1
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Prior art keywords
tert
weight
butyl
acrylamide
methacrylic acid
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PCT/EP2004/013984
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German (de)
English (en)
Inventor
Son Nguyen-Kim
Claudia Wood
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Basf Aktiengesellschaft
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Priority to EP04803650A priority Critical patent/EP1694728B1/fr
Priority to US10/581,884 priority patent/US7858076B2/en
Priority to JP2006543468A priority patent/JP2007514031A/ja
Priority to CA002547754A priority patent/CA2547754A1/fr
Priority to DE502004007861T priority patent/DE502004007861D1/de
Publication of WO2005058989A1 publication Critical patent/WO2005058989A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/007—Preparations for dry skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/04—Preparations for care of the skin for chemically tanning the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/006—Antidandruff preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate

Definitions

  • the present invention relates to copolymers which contain tert-butyl (meth) acrylate, at least one ⁇ , ⁇ -ethylenically unsaturated compound containing amide groups and acrylic acid in copolymerized form, cosmetic and pharmaceutical compositions which contain at least one such copolymer and the use of these copolymers.
  • Polymers with film-forming properties have found a wide variety of applications in the pharmaceutical and cosmetics sectors. In pharmacy, for example, they serve as coating agents or binders for solid pharmaceutical forms. In cosmetics, polymers with film-forming properties are u. a. used to strengthen, improve the structure and shape of the hair. They serve, for example, as conditioners to improve dry and wet combability, feel, shine and appearance, and to give the hair antistatic properties. Requirements placed on film-forming polymers for use as setting resins are e.g. These include, for example, strong strengthening (even with high air humidity), elasticity, washability from the hair, compatibility in the formulation and a pleasant handle on the hair treated with it. It is often difficult to provide products with a complex property profile.
  • DE-A-32 27 334 (EP-A-0 100 890) describes copolymers which, by radical copolymerization of a) at least one C 2 -C 20 - (meth) acrylic acid alkyl ester, for. B. tert-butyl (meth) acrylate, b) at least one water-soluble nitrogen-containing monomer, for. B. an N-vinyl lactam, c) at least one monomer with cationic groups and d) at least one free-radically polymerizable carboxylic acid.
  • DE-A-36 27 970 and DE-A-40 31 912 describe terpolymers of vinylpyrrolidone, tert-butyl (meth) acrylate and acrylic acid or methacrylic acid and their use in hair treatment agents.
  • DE-A-43 14 305 describes a hair fixative which, as a film former, is a copolymer based on tert-butyl acrylate or tert-butyl (meth) acrylate, acrylic acid or methacrylic acid and a radically copolymerizable monomer which comprises a homopolymer with a Glass temperature delivers ⁇ 30 ° C contains.
  • DE-A-100 08 263 describes a cosmetic composition which contains at least one water-soluble or water-dispersible polymer which contains at most 50% by weight of at least one tert-butyl ester and / or N-tert-butyl amide of an ⁇ , ⁇ -ethylenic unsaturated carboxylic acid and at least one N-vinylamide and / or vinyl lactam and at least one polymerizable compound having a cationogenic and / or cationic group in copolymerized form.
  • WO 01/62809 describes a cosmetic agent which contains at least one water-soluble or water-dispersible polymer which
  • ⁇ , ⁇ -ethylenically unsaturated compound which may be compounds having at least one anionogenic and / or anionic group per molecule
  • EP-A-0 062 002 describes a hair fixation preparation which contains a terpolymer of an N-alkyl (meth) acrylamide, a CC 4 -alkyl ester or CC -hydroxyalkyl ester of (meth) acrylic acid and acrylic acid of methacrylic acid.
  • a terpolymer of an N-alkyl (meth) acrylamide, a CC 4 -alkyl ester or CC -hydroxyalkyl ester of (meth) acrylic acid and acrylic acid of methacrylic acid is not disclosed.
  • the unpublished German patent application P 102 61 750.3 describes an ampholytic copolymer obtained by radical copolymerization of a) at least one ethylenically unsaturated compound with at least one anionogenic and / or anionic group, b) at least one ethylenically unsaturated compound with at least one cationogenic and / or cationic Group, c) at least one unsaturated compound containing amide groups
  • polyelectrolyte complexes which contain such an ampholytic copolymer, and cosmetic or pharmaceutical compositions based on these ampholytic copolymers and polyelectrolyte complexes.
  • compositions in an aqueous medium in the presence of at least one polymeric anionic dispersant D). They are suitable as conditioning agents for cosmetic preparations, in particular shampoos.
  • the unpublished German patent application 102 37 378.7 describes a cosmetic or pharmaceutical composition which comprises at least one polyelectrolyte complex which, as component A1), has at least one water-soluble or water-dispersible copolymer with cationogenic groups, the vinylimidazole and / or a derivative thereof and at least one further with it contains copolymerizable monomer in copolymerized form and contains as component A2) at least one acid group-containing polymer.
  • copolymers which are obtainable by free-radical polymerization of a monomer mixture comprising are particularly suitable for the abovementioned requirements
  • R 1 represents H or CC 4 alkyl
  • R 2 and R 3 independently of one another represent H or CC 4 alkyl or R 2 and R 3 together with the nitrogen atom to which they are attached can also represent a 4- to 7-membered heterocycle, with the proviso that the sum of the carbon atoms of the radicals R 1 , R 2 and R 3 is at most 4, and
  • water-soluble monomers and polymers are understood to mean monomers and polymers which dissolve at least 1 g / l in water at 20 ° C.
  • Water-dispersible monomers and polymers are understood to mean monomers and polymers which disintegrate into dispersible particles using shear forces, for example by stirring.
  • Hydrophilic monomers are preferably water-soluble or at least water-dispersible.
  • the copolymers according to the invention are generally water-soluble.
  • the copolymers according to the invention are particularly advantageously suitable for use in cosmetic compositions, in particular in hair treatment compositions. They are preferably used to create elastic hairstyles with strong strength at the same time. In addition, they are advantageously distinguished both by good propellant gas compatibility and by good solubility in water or aqueous / alcoholic solvent mixtures. They can therefore be formulated both for hair sprays containing a high amount of propellant gas (VOC at least 85% by weight) and for formulations with low VOC values (generally not more than 55% by weight, based on the total weight of the composition). In any case, the hair spray formulations are characterized by very good sprayability.
  • some of the monomers a) can be replaced by at least one monomer f).
  • up to 50% by weight of the monomers of component a) can therefore be replaced by at least one CC 3 alkyl methacrylate and / or hydroxy-C 3 alkyl methacrylate.
  • Suitable CrC 3 alkyl methacrylates and hydroxy-CrCs alkyl methacrylates are described below for component f).
  • Ethyl methacrylate is preferably used.
  • the copolymers according to the invention contain, as component a), tert-butyl acrylate and / or tert-butyl methacrylate as copolymerized units.
  • tert-butyl methacrylate is not used alone as component a).
  • Copolymers are therefore preferred, component a) comprising or consisting of tert-butyl acrylate.
  • the copolymers according to the invention preferably contain 30 to 90% by weight, particularly preferably 40 to 85% by weight, based on the total weight of the monomers used for the polymerization, of at least one compound a) copolymerized.
  • the copolymers contain at least one amide of an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid of the general formula I polymerized.
  • the radicals R 2 and R 3 are preferably both H or one of the radicals R 2 and R 3 is H and the other is CC 4 -alkyl.
  • the amides of the general formula I are preferably derived from acrylic acid, methacrylic acid or ethacrylic acid as ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid.
  • Component b) is preferably selected from acrylic acid amide, methacrylic acid amide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) acrylic!
  • Component b) preferably comprises methacrylic acid amide and / or N- (tert-butyl) acrylamide or consists of one of these components or a mixture of methacrylic acid amide and N- (tert-butyl) acrylamide.
  • the copolymers according to the invention preferably contain 3 to 50% by weight, particularly preferably 5 to 40% by weight, in particular 10 to 35% by weight, based on the total weight of the monomers used for the polymerization, of at least one compound of component b) ,
  • acrylic acid c) can be used in partially or completely deprotonated form. Then their counterions are preferably derived from bases, as described below for adjusting the pH during the polymerization or the polymers obtained.
  • the copolymers according to the invention consist only of monomer units of the aforementioned monomers a), b) and c). In further training In embodiments, the copolymers according to the invention contain additional monomers copolymerized. Suitable additional monomers are listed below.
  • the copolymers then preferably contain up to 25% by weight, particularly preferably up to 20% by weight, in particular up to 15% by weight, based on the total weight of the monomers used for the polymerization, polymerized methacrylic acid. If methacrylic acid is used for the polymerization, then preferably in an amount of at least 1% by weight, particularly preferably at least 5% by weight.
  • the copolymers according to the invention may additionally contain at least one compound having a free-radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond and at least one cationogenic and / or cationic group per molecule.
  • the cationogenic or cationic groups of component e) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups and quaternary ammonium groups.
  • the nitrogen-containing groups are preferably tertiary amino groups.
  • the compounds e) are preferably used in the uncharged form for the polymerization. However, use in a charged form is also suitable.
  • Charged cationic groups can e.g. B. from the amine nitrogen by protonation, for. B. with monovalent or polyvalent carboxylic acids, such as lactic acid or tartaric acid, or mineral acids, such as phosphoric acid, sulfuric acid and hydrochloric acid.
  • Component e) is preferably selected from esters ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, which may be mono- or dialkylated on amine nitrogen, amides ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines, which have at least one have primary or secondary amino group, N, N-diallylamine, N, N-diallyl-N-alkylamines and their derivatives, vinyl- and allyl-substituted nitrogen heterocycles, vinyl- and allyl-substituted heteroaromatic compounds and mixtures thereof.
  • Suitable as compounds e) are the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols.
  • Preferred amino alcohols are C 2 -C 2 -amino alcohols which are CC 8 -mono- or -dialkylated on the amine nitrogen.
  • an acid component of these esters are, for. B. acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and their mixtures are preferred. see used.
  • Particularly preferred compounds c2) are N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N- (n-propyl) aminoethyl (meth) acrylate, N- (n-butyl) aminoethyl (meth) acrylate, N - (tert-butyl) aminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate,
  • N- (tert-butyl) aminoethyl acrylate and N- (tert-butyl) aminoethyl methacrylate are used as compound e).
  • Suitable monomers e) are also the amides of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Diamines which have a tertiary and a primary or secondary amino group are preferred.
  • Preferred monomers e) are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl ] acrylamide and N- [4- (dimethylamino) cyclohexyl] methacrylamide used. N- [3- (dimethylamino) propyl] acrylamide and / or N- [3- (dimethylamino) propyl
  • Suitable monomers e) are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts.
  • Alkyl is preferably CrC 2 alkyl.
  • Suitable monomers e) are further vinyl and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinylimidazole derivatives, for.
  • N-vinyl-2-methylimidazole vinyl and allyl substituted heteroaromatic compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.
  • Suitable monomers e) are also N-vinylimidazoles of the general formula (I), in which R 1 to R 3 are hydrogen, CC 4 alkyl or phenyl
  • the compounds of component e) are particularly preferably selected from N- (tert-butylamino) ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- [3- (dimethylamino) propyl] (meth) acrylamide, Vinylimidazole and mixtures thereof.
  • the copolymers according to the invention preferably contain up to 25% by weight, particularly preferably up to 20% by weight, in particular up to 10% by weight, based on the total weight of the monomers used for the polymerization, at least one monomer e) polymerized. If a monomer e) is used, then preferably in an amount of at least 1% by weight, particularly preferably at least 2% by weight.
  • the copolymers according to the invention may additionally contain at least one copolymerized monomer f) which is different from components a) to e) and copolymerized therewith.
  • component f) is selected from component a), various esters, ß-ethylenically unsaturated mono- and dicarboxylic acids with C ⁇ .-C 30 alkanols and -C 30 alkanediols, ⁇ amides, ß-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 amino alcohols which have a primary or secondary amino group, N-vinyl lactams, N-vinyl amides of saturated monocarboxylic acids, primary amides ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids different from component b) and their N-alkyl and N , N-dialkyl derivatives, esters of vinyl alcohol and allyl alcohol with C 1 -C 30 -
  • N-vinyl lactams suitable as monomers f) are unsubstituted N-vinyl lactams and
  • N-vinyl lactam derivatives e.g. B. can have one or more C Ce alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc.
  • N-vinylpyrrolidone N-vinylpiperidone, N-vinylcaprolactam
  • the copolymers according to the invention contain no N-vinyl lactams polymerized.
  • N-vinylamide compounds suitable as monomers f) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide,
  • the copolymers according to the invention contain no N-vinylamide compounds copolymerized.
  • Suitable additional monomers f) are also 2-hydroxyethyl acrylate,
  • Suitable additional monomers f) are furthermore 2-hydroxyethylacrylamide, 2-hydroxyethyl methacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide, 2-hydroxypropyl methacrylamide, 3-hydroxypropylacrylamide, 3-hydroxypropyl methacrylamide, 3-hydroxybutyl acrylamide, 3-hydroxybutyl methacrylamide, 4-hydroxybutyl methacrylamide, 4-hydroxyl acrylate , 6-Hydroxyhexylacrylamid, 6-Hydroxyhexylmethacrylamid, 3-Hydroxy-2-ethylhexylacrylamid and 3-Hydroxy-2-ethylhexylmethacrylamid.
  • Suitable monomers f) are also polyether acrylates, which in the context of this invention are generally understood to mean esters, ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with polyetherols.
  • Suitable polyetherols are linear or branched substances which have terminal hydroxyl groups and contain ether bonds. Generally they have a molecular weight in the range of about 150 to 20,000.
  • Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
  • Suitable alkylene oxides for the production of alkylene oxide copolymers are, for. B.
  • alkylene oxide copolymers can contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks. Ethylene oxide / propylene oxide copolymers are preferred.
  • Preferred component f) are polyether acrylates of the general formula II
  • H 2 C CC Y2 (CH 2 CH 2 0) k (CH 2 CH (CH 3 ) 0), R
  • k and I independently of one another represent an integer from 0 to 1000, the sum of k and I being at least 5,
  • R 4 represents hydrogen, CC 3 o-alkyl or C 5 -C 8 cycloalkyl
  • R 5 represents hydrogen or CC 8 alkyl
  • Y 2 represents O or NR 6 , where R 6 represents hydrogen, d-caoalkyl or C 5 -C 8 cycloalkyl,
  • K is preferably an integer from 1 to 500, in particular 3 to 250.
  • I is preferably an integer from 0 to 100.
  • R 5 is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, especially for hydrogen, methyl or ethyl.
  • R 4 in formula II preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, Palmityl or stearyl.
  • Y 2 in formula II is preferably O or NH.
  • Suitable polyether acrylates f) are e.g. B. the polycondensation products of the aforementioned ⁇ , ⁇ -ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols.
  • Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule such as water or a short-chain alcohol R 4 - OH.
  • the alkylene oxides can be used individually, alternately in succession or as a mixture.
  • the polyether acrylates e) can be used alone or in mixtures for producing the polymers used according to the invention.
  • Suitable additional monomers f) are methyl (meth) acrylate, methyl ethacrylate, ethyl (meth) acrylate, 2-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, isopentyl acrylate, neopentyl acrylate, ethyl ethacrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ethacrylate, n-octyl (meth) acrylate, 1, 1, 3,3-tetramethylbutyl (meth) acrylate, ethylhexyl ( meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl
  • Suitable additional monomers f) are also N- (n-butyl) methacrylamide, N- (sec-butyl) methacrylamide, N- (tert-butyl) methacrylamide, N- (n-pentyl) (meth) acrylamide, N- (n-Hexyl) (meth) acrylamide, N- (n-heptyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (tert.-octyl) (meth) acrylamide N- (1st , 1, 3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n undecyl) (meth) acrylamide,
  • Suitable additional monomers f) are also vinyl acetate, vinyl propionate, vinyl butyrate and mixtures thereof.
  • Suitable additional monomers f) are also ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • the aforementioned additional monomers f) can be used individually or in the form of any mixtures.
  • the copolymers according to the invention preferably contain in copolymerized form at least one compound f) which is selected from dC 3 -alkyl methacrylates, hydroxy-dC 3 -alkyl methacrylates and mixtures thereof. Ethyl methacrylate, hydroxyethyl methacrylate and mixtures thereof are particularly preferred. In particular, ethyl methacrylate is used.
  • the copolymers according to the invention preferably contain these monomers in an amount of at most 50% by weight, particularly preferably at most 45% by weight, based on the total weight of compounds of component a) and these compounds f).
  • the copolymers according to the invention preferably contain up to 25% by weight, more preferably up to 20% by weight, in particular up to 15% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer f) polymerized. If a monomer f) is used, then preferably in an amount of at least 0.1% by weight, particularly preferably at least 1% by weight and in particular at least 5% by weight.
  • the copolymers according to the invention can contain at least one crosslinker, i.e. H. contain a compound with two or more than two ethylenically unsaturated, non-conjugated double bonds in copolymerized form.
  • Crosslinking agents are preferably used in an amount of 0.01 to 3% by weight, particularly preferably 0.1 to 2% by weight, based on the total weight of the monomers used for the polymerization.
  • Suitable crosslinkers g) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
  • the OH groups of the underlying alcohols can be fully or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
  • Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , But-2-en-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1 , 12-dodecanediol, neopentyl glycol, 3-methylpentane, 5-diol, 2,5-dimethyl-1, 3-hexanedioi, 2,2,4-trimethyM, 3-pentanediol, 1, 2-cyclohexane
  • block copolymers of ethylene oxide or propylene oxide or copolymers which contain ethylene oxide and propylene oxide groups can also be incorporated, be used.
  • underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1, 2,6-hexanetriol, triethoxycyanoic acid, sorbitan, sugars such as sucrose, glucose, mannose.
  • the polyhydric alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide.
  • the polyhydric alcohols can also first be converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.
  • crosslinkers g) are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • ethylenically unsaturated C 3 -C 6 -carboxylic acids for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamon alcohol , Citronellol,
  • Crotyl alcohol or cis-9-octadecen-1-ol can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • crosslinkers g) are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • crosslinkers g) are urethane diacrylates and urethane polyacrylates, such as z. B. are commercially available under the name Laromer®.
  • Suitable as crosslinkers g) are also straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to aliphatic hydrocarbons, e.g. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights of 200 to 20,000.
  • crosslinking agents g) are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines.
  • Such amines are, for example, 1, 2-diaminomethane, 1, 2-diaminoethane, 1, 3-diaminopropane, 1,4-diaminobutane, 1, 6-diaminohexane, 1, 12-dodecanediamine, piperazine, diethylene triamine or isophorone diamine.
  • the amides of allylamine and unsaturated carboxylic acid are also suitable.
  • ren such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.
  • Triallylamine and triallylmonoalkylammonium salts e.g. B. triallylmethylammonium chloride or methyl sulfate, suitable as crosslinking agent g).
  • N-vinyl compounds of urea derivatives at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaric acid diamide, eg. B. N.N'-divinylethyleneurea or N, N'-divinylpropyleneurea.
  • crosslinkers g) are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • Mixtures of the aforementioned compounds g) can of course also be used.
  • Water-soluble crosslinking agents g) are preferably used.
  • Crosslinking agents g) used with particular preference are, for example, methylenebisacrylamide, triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic acid esters of polyalkyleneoxides with polyalkyleneoxides Ethylene oxide and / or propylene oxide and / or epichlorohydrin have been implemented.
  • a preferred embodiment are copolymers which consist of repeating units of tert-butyl acrylate, - methacrylic acid amide and / or N- (tert-butyl) acrylamide, and acrylic acid
  • a further preferred embodiment are copolymers which consist of repeating units of tert-butyl acrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, acrylic acid and methacrylic acid
  • copolymers which consist of repeating units of tert-butyl acrylate, N-acryloylmorpholine or N, N-dimethylacrylamide and acrylic acid
  • a further preferred embodiment is copolymers which consist of repeating units of tert-butyl acrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide and / or N-acryloylmorpholine and / or N, N-dimethylacrylamide and acrylic acid consist.
  • a further preferred embodiment is copolymers which consist of repeating units of tert-butyl acrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide and / or N-acryloylmorpholine and / or N, N-dimethylacrylamide, acrylic acid and methacrylic acid
  • a further preferred embodiment are copolymers which consist of repeating units of tert-butyl acrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, N-vinylpyrrolidone and acrylic acid
  • a further preferred embodiment is copolymers which consist of repeating units of tert-butyl acrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, N-vinylpyrrolidone, acrylic acid and methacrylic acid
  • copolymers which consist of repeating units of tert-butyl acrylate, tert-butyl methacrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, and acrylic acid
  • a further preferred embodiment are copolymers which consist of repeat units of tert-butyl acrylate, tert-butyl methacrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, acrylic acid and methacrylic acid
  • copolymers which consist of repeating units of tert-butyl acrylate and / or tert-butyl methacrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, acrylic acid, methacrylic acid and - N- (tert-butyl) aminoethyl (meth) acrylate or N- [3- (dimethylamino) propyl] methacrylamide or N-vinylimidazole
  • tert-butyl acrylate and / or tert-butyl methacrylate b) methacrylic acid amide and / or N- (tert-butyl) acrylamide, c) acrylic acid and f) at least one compound which is selected from dC 3 -alkyl methacrylates, hydroxy -dC 3 -alkyl methacrylates and mixtures thereof,
  • copolymerized form with the proviso that the proportion by weight of component a) is equal to or greater than the proportion by weight of component f).
  • a preferred embodiment are copolymers which
  • tert-butyl acrylate a) tert-butyl acrylate, b) methacrylic acid amide and / or N- (tert-butyl) acrylamide, c) acrylic acid, d) methacrylic acid, f) ethyl methacrylate and / or hydroxyethyl methacrylate
  • a particularly preferred embodiment is copolymers which consist of repeating units of tert-butyl acrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, acrylic acid and - ethyl methacrylate
  • copolymers which consist of repeating units of tert-butyl acrylate, methacrylic acid amide and / or N- (tert-butyl) acrylamide, acrylic acid, methacrylic acid and ethyl methacrylate
  • copolymers which, based in each case on the total weight of the monomers used for the polymerization,
  • methacrylic acid amide and / or N- (tert-butyl) acrylamide 5 to 30% by weight, preferably 5 to 15% by weight, acrylic acid and 0 to 25% by weight, preferably 5 to 20% by weight, methacrylic acid
  • the preparation of the copolymers according to the invention can e.g. B. by solution, precipitation, suspension or emulsion polymerization. Such methods are known in principle to the person skilled in the art. Production by solution polymerization is preferred.
  • Preferred solvents for the polymerization are aqueous solvents, such as water, and mixtures of water with water-miscible solvents, for example alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n- Hexanol and cyclohexanol as well as glycols such as ethylene glycol, propylene glycol and butylene glycol and the methyl or ethyl ether of the dihydric alcohols, diethylene glycol, triethylene glycol, polyethylene glycols with number average molecular weights up to about 3000, glycerol and dioxane.
  • all inorganic or organic bases are suitable for adjusting the pH before, during or after the polymerization, in particular those which, apart from any salt formation, do not react with the monomers. Suitable bases are e.g. B.
  • alkali and alkaline earth metal hydroxides ammonia and primary, secondary and tertiary amines, such as triethylamine, and amino alcohols, such as triethanolamine, methyldiethanolamine, dimethylethanolamine or 2-amino-2-methylpropanol.
  • the polymerization temperatures are preferably in a range from about 30 to 120 ° C., particularly preferably 40 to 100 ° C.
  • the polymerization is usually carried out under atmospheric pressure, but it can also take place under reduced or elevated pressure.
  • a suitable pressure range is between 1 and 5 bar.
  • the monomers can be polymerized with the aid of initiators which form free radicals.
  • the peroxo and / or azo compounds customary for this purpose can be used as initiators for the radical polymerization, for example alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert.- Butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbamate, bis- (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl peroxide, tert-butyl peroxide tert-amyl peroxide, tert-butyl hydroperoxide,
  • the polymerization can be carried out in the presence of at least one regulator.
  • the usual connections known to those skilled in the art such as, for example, B. sulfur compounds, e.g. B. mercaptoethanol,
  • 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan and tribromochloromethane or other compounds which have a regulating effect on the molecular weight of the polymers obtained are used.
  • a preferred regulator is cysteine.
  • the polymerization (main polymerization) can be followed by a post-polymerization step.
  • the post-polymerization can be carried out in the presence of the same or a different initiator system as the main polymerization.
  • the postpolymerization preferably takes place at least at the same temperature, preferably at a higher temperature than the main polymerization.
  • the reaction mixture can be subjected to steam stripping or steam distillation after the polymerization or between the first and second polymerization steps.
  • an organic solvent used in the preparation of the polymers, this can be done by customary methods known to those skilled in the art, e.g. B. can be removed by distillation under reduced pressure.
  • the liquid polymer compositions obtained can be obtained by various drying processes, such as. B. spray drying, fluidized spray drying, roller drying or freeze drying can be transferred in powder form. Spray drying is preferably used.
  • the polymer dry powders obtained in this way can advantageously be converted again into an aqueous solution or dispersion by dissolving or redispersing them in water. Powdery copolymers have the advantage of better storability, easier transportation and usually show a lower tendency for germ infestation. These generally include anionic, cationic, amphoteric and neutral polymers.
  • copolymers described above are extremely suitable for the production of cosmetic and pharmaceutical agents. They serve z. B. as polymeric film formers in personal care preparations, which includes use in cosmetic preparations for keratinous surfaces such as skin, hair, nails and also oral care preparations. They can be used universally in a wide variety of cosmetic preparations and can be formulated and are compatible with the usual components.
  • the copolymers according to the invention are particularly suitable for producing hair cosmetic compositions. Compared to conventional polymers known from the prior art, they are advantageously suitable for producing elastic hairstyles while at the same time being strongly strengthened (even at high atmospheric humidity).
  • copolymers according to the invention are also notable for good propellant gas compatibility, good solubility in water or aqueous / alcoholic solvent mixtures, suitability for use in low-VOC formulations and good washability.
  • they usually also have good conditioning properties, i.e. H. they improve treated hair in its sensible properties such as feel, volume, manageability etc.
  • Hair spray formulations based on the copolymers according to the invention are distinguished by good rheological properties and good sprayability.
  • the agents according to the invention have a cosmetically or pharmaceutically acceptable carrier B), which is selected from
  • water-miscible organic solvents preferably C 2 -C 4 -alkanols, in particular ethanol
  • the agents according to the invention have z. B. an oil or fat component B), which is selected from: hydrocarbons of low polarity, such as mineral oils; linear saturated hydrocarbons, preferably with more than 8 carbon atoms, such as tetra-decane, hexadecane, octadecane, etc .; cyclic hydrocarbons such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as. B.
  • hydrocarbons of low polarity such as mineral oils
  • linear saturated hydrocarbons preferably with more than 8 carbon atoms, such as tetra-decane, hexadecane, octadecane, etc .
  • cyclic hydrocarbons such as decahydronaphthalene
  • branched hydrocarbons animal and vegetable oils
  • To grow Wax esters
  • Petroleum jelly Petroleum jelly
  • esters of CC 2 -monoalcohols with CC 22 -monocarboxylic acids such as isopropyl isostearate, n-propyl myristate, iso-propyl myristate, n-propyl palmitate, iso-propyl palmitate, hexaconyl palmitate, octacosanyl palmitate, triacontanyl palatate, triacontanyl palmitate, dacotanyl palacate, Octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates such as d-do salicylates, e.g.
  • Suitable silicone oils B) are e.g. B. linear polydimethylsiloxanes, poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof.
  • the number average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxanes) is preferably in a range from about 1000 to 150,000 g / mol.
  • Preferred cyclic siloxanes have 4- to 8-membered rings.
  • Suitable cyclic siloxanes are e.g. B. commercially available under the name Cyclomethicone.
  • Preferred oil or fat components B) are selected from paraffin and paraffin oils; Petroleum jelly; natural fats and oils, such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, pork lard, walnut, spermacet oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, evening primrose oil; Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cetyl alcohol; Fatty acids such as myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid and various saturated, unsaturated and substituted fatty acids; Waxes such as beeswax, carnauba wax, candililla wax, walrus and mixtures of the oil or fat components mentioned above.
  • Suitable cosmetically and pharmaceutically acceptable oil or fat components B) are described in Karl-Heinz Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Verlag Wegig, Heidelberg, pp. 319-355, to which reference is made here.
  • Suitable hydrophilic carriers B) are selected from water, 1-, 2- or polyhydric alcohols with preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.
  • the cosmetic agents according to the invention can be skin cosmetic, hair cosmetic, dermatological, hygienic or pharmaceutical agents. Because of their film-forming properties, the copolymers and polyelectrolyte complexes described above are particularly suitable as additives for hair and skin cosmetics.
  • agents according to the invention are preferably in the form of a spray, gel, foam, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
  • the cosmetically or pharmaceutically active agents according to the invention can additionally contain cosmetically and / or dermatologically active substances and auxiliaries.
  • Typical thickeners in such formulations are crosslinked polyacrylic acids and their derivatives, polysaccharides and their derivatives, such as xanthan gum, agar agar, alginates or tyloses, cellulose derivatives, e.g. B. carboxymethyl cellulose or hydroxy carboxymethyl cellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinyl pyrrolidone.
  • Nonionic thickeners are preferably used.
  • Suitable cosmetically and / or dermatologically active ingredients are e.g. B. coloring agents, skin and hair pigmentation agents, tinting agents, tanning agents, bleaching agents, keratin-curing substances, antimicrobial agents, light filter agents, repellent agents, hyperemising agents, keratolytic and keratoplastic agents, anti-dandruff agents, anti-inflammatory agents, keratinizing agents, as antioxidant agents Radical scavengers active ingredients, skin moisturizing or moisturizing substances, lipid replenishing active ingredients, anti-inflammatory or anti-allergic active ingredients and mixtures thereof.
  • Artificially tanning agents that are suitable for tanning the skin without natural or artificial radiation with UV rays are, for. B. dihydroxyacetone, alloxane and walnut shell extract.
  • Suitable keratin-curing substances are usually active substances, such as those used in antiperspirants, such as. As potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.
  • Antimicrobial agents are used to destroy microorganisms or inhibit their growth and thus serve both as a preservative and as a deodorizing substance that reduces the development or intensity of body odor. These include e.g. B.
  • Suitable light filter agents are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are e.g. B.
  • 2,4,6-triaryl-1, 3,5-triazines in which the aryl groups can each carry at least one substituent, which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof ,
  • substituent which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof
  • substituent which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof
  • p-aminobenzoic acid esters cinnamic acid esters, benzophenones, camphor derivatives and pigments which block UV rays, such as titanium dioxide, talc and zinc oxide.
  • Suitable repellent agents are compounds that are able to deter or drive away certain animals, especially insects,
  • Suitable hyperemising substances that stimulate the blood flow to the skin are, for.
  • Suitable keratolytic and keratoplastic substances are.
  • Suitable anti-dandruff agents are, for. B.
  • Suitable anti-inflammatory drugs that counteract skin irritation are, for. B. allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.
  • the cosmetic agents according to the invention can contain at least one cosmetically or pharmaceutically acceptable polymer as a cosmetic and / or pharmaceutical active ingredient (as well as optionally as an adjuvant).
  • Anionic polymers preferred as additional polymers are, for example, homopolymers and copolymers of acrylic acid and methacrylic acid and their salts.
  • This also includes cross-linked polymers of acrylic acid, as are available under the INCI name Carbomer.
  • Crosslinked homopolymers of acrylic acid of this type are commercially available, for example, under the name Carbopol® from BF GOODRICH.
  • suitable additional anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas.
  • Particularly suitable polymers are copolymers of (meth) acrylic acid and polyether acrylates, the polyether chain being terminated with a C 8 -C 30 alkyl radical. There- to count e.g. B. Acrylate / Beheneth-25 methacrylate copolymers, which are available under the name Aculyn® from Rohm and Haas.
  • Particularly suitable polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (for example Luvimer® MAE), copolymers of N-tert.-butyl acrylamide, Ethyl acrylate, acrylic acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally other vinyl esters (e.g. Luviset® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, e.g. B.
  • Meth (acrylic acid), C 4 -C 30 alkyl vinyl ester, C 4 -C 30 alkyl vinyl ether and hyaluronic acid examples are also vinyl acetate / crotonic acid copolymers, such as are commercially available under the names Resyn® (National Starch) and Gafset® (GAF), and vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF) , Other suitable polymers are the vinyl pyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester.
  • anionic polymers examples are also vinyl acetate / crotonic acid copolymers, such as are commercially available under the names Resyn® (National Starch) and Gafset® (GAF), and vinylpyrrolidone / vinyl acrylate copoly
  • the group of suitable anionic polymers also includes, for example, Balance® CR (National Starch; Acrylate Copolymer), Balance® 0/55 (National Starch; Acrylate Copolymer), Balance® 47 (National Starch; Octylacrylamid / Acrylate / Butylaminoethylmethacrylate-Copolymer) , Aquaflex® FX 64 (ISP; isobutylene / ethyl-maleimide / hydroxyethylmaleimide copolymer), Aquaflex® SF-40 (ISP / National Starch; VP / Vinyl Caprolactam / DMAPA Acrylate Copolymer), Allianz® LT-120 (ISP; Rohm &Haas; Acrylate / C1-2 succinate / hydroxyacrylate copolymer), Aquarez® HS (Eastman; Polyester-1), Diaformer® Z-400 (Clariant; methacryloylethylbetaine / methacrylate
  • Suitable additional polymers are also the terpolymers described in US Pat. No. 3,405,084 made from vinyl pyrrolidone, CC 10 alkyl, cycloalkyl and aryl (meth) acrylates and acrylic acid.
  • Suitable additional polymers are also the terpolymers described in EP-A-0 257 444 and EP-A-0 480 280 made of vinylpyrrolidone, tert-butyl (meth) acrylate and (meth) acrylic acid.
  • Suitable additional polymers are also the copolymers described in DE-A-42 23 066, which contain at least one (meth) acrylic ester, (meth) acrylic acid and N-vinylpyrrolidone and / or N-vinylcaprolactam in copolymerized form. Reference is hereby made to the disclosure of these documents.
  • Suitable polymers containing carboxylic acid groups are furthermore polyurethanes containing carboxylic acid groups.
  • EP-A-636361 discloses suitable block copolymers with polysiloxane blocks and polyurethane / polyurea blocks which have carboxylic acid and / or sulfonic acid groups.
  • Suitable silicone-containing polyurethanes are also described in WO 97/25021 and EP-A-751 162.
  • Suitable polyurethanes are also described in DE-A-42 25 045, to which reference is made in full here. In principle, these polyurethanes are composed of at least one compound which contains two or more active hydrogen atoms per molecule,
  • Component i) is e.g. B. diols, diamines, amino alcohols, and mixtures thereof.
  • the molecular weight of these compounds is preferably in a range from about 56 to 280. If desired, up to 3 mol% of the compounds mentioned can be replaced by triols or triamines.
  • Useful diols i) are e.g. B. ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethylol, di-, tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof. Neopentyl glycol and / or cyclohexanedimethylol are preferably used.
  • Suitable amino alcohols i) are e.g. B.
  • Suitable diamines i) are e.g. B. ethylenediamine, propylenediamine, 1, 4-diaminobutane, 1, 5-diaminopentane and 1, 6-diaminohexane and ⁇ , ⁇ -diaminopolyether, which can be prepared by amination of polyalkylene oxides with ammonia.
  • Component i) can also be a polymer having a number average molecular weight in the range from about 300 to 5000, preferably about 400 to 4000, in particular 500 to 3000.
  • Useful polymers i) are, for. B. polyester diols, polyetherols and mixtures thereof.
  • Polyetherols are preferably polyalkylene glycols, e.g. B. polyethylene glycols, polypropylene glycols, polytetrahydrofurans etc, block copolymers of ethylene oxide and propylene oxide or block copolymers of ethylene oxide, propylene oxide and butylene oxide, which contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks.
  • Suitable polytetrahydrofurans i) can by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, such as. As sulfuric acid or fluorosulfuric acid can be produced. Such production processes are known to the person skilled in the art.
  • Usable polyester diols i) preferably have a number average molecular weight in the range from about 400 to 5000, preferably 500 to 3000, in particular 600 to 2000.
  • Suitable polyester diols i) are all those which are customarily used for the production of polyurethanes, in particular those based on aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, Na- or K-sulfoisophthalic acid etc., aliphatic dicarboxylic acids, such as adipic acid or succinic acid, etc. ., and cycloaliphatic dicarboxylic acids, such as 1, 2-, 1, 3- or 1, 4-cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, Na- or K-sulfoisophthalic acid etc.
  • aliphatic dicarboxylic acids such as adipic acid or succinic acid, etc. .
  • cycloaliphatic dicarboxylic acids such as 1, 2-, 1, 3- or 1, 4-cyclohexanedicarboxy
  • diols are aliphatic diols, such as ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane, etc.
  • Suitable compounds ii) which have two active hydrogen atoms and at least one carboxylic acid group per molecule are, for. B. dimethylolpropanoic acid and mixtures containing dimethylolpropanoic acid.
  • Component iii) is a customary aliphatic, cycloaliphatic and / or aromatic polyisocyanate, such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their mixtures of isomers, o- and m-xylylene diisocyanate, 1 , 5-naphthylene diisocyanate, 1, 4-cyclohexylene diisocyanate, dicyclohexyl methane diisocyanate and mixtures thereof, in particular isophorone diisocyanate and / or dicyclohexyl methane diisocyanate. If desired, up to 3 mol% of the compounds mentioned can be replaced by triisocyanates.
  • Suitable additional polymers are also cationic polymers. These include e.g. B. polymers with the name Polyquaternium according to INCI, z. B. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ N-11), copolymers of copolymers / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (Polyquatemium-4 and -10), acrylamido copolymers (Polyquatemium-7) and chitosan.
  • Suitable cationic (quaternized) polymers are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers which are formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxy ethyl cellulose with cationic groups) and cationic plant-based polymers, e.g. B. guar polymers, such as the Jag ⁇ ar ⁇ brands from Rhodia.
  • Suitable additional polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer® (National Starch)
  • Octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers as are disclosed, for example, in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451.
  • zwitterionic polymers are preferred zwitterionic polymers.
  • Other suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).
  • Neutral polymers suitable as additional polymers are e.g. B. polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, polyaspartic acid derivatives.
  • These include, for example, Luviflex® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, from BASF).
  • Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinylcaprolactam, eg. B. Luviskol® Plus (BASF), or polyvinylpyrrolidone and their copolymers, in particular with vinyl esters such as vinyl acetate, for. B. Luviskol® VA 37 (BASF); Polyamides, e.g. B. based on itaconic acid and aliphatic diamines, such as z. B. are described in DE-A-43 33 238.
  • Suitable polymers are also nonionic, siloxane-containing, water-soluble or
  • -Dispersible polymers e.g. B. polyether siloxanes, such as Tegopren® (from Goldschmidt) or Belsil® (from Wacker).
  • the formulation base of pharmaceutical agents according to the invention preferably contains pharmaceutically acceptable excipients.
  • the excipients known to be usable in the field of pharmacy, food technology and adjacent areas are pharmaceutically acceptable, in particular the excipients listed in relevant pharmacopoeias (e.g. DAB Ph. Eur. BP NF) and other excipients, the properties of which do not conflict with physiological application.
  • Suitable auxiliaries can be: lubricants, wetting agents, emulsifying and suspending agents, preserving agents, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film-forming agents, gelling agents, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation compounds, accelerators, ammonium, pigment, Regreasing and Superfatting agents, ointment, cream or oil base materials, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, thickeners, waxes, plasticizers, white oils.
  • a design in this regard is based on professional knowledge, such as that shown in Fiedler, HP Lexikon der Hilfsstoff für Pharmazie, Kosmetik und adjacent areas, 4th ed., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.
  • the active ingredients can be mixed or diluted with a suitable excipient.
  • Excipients can be solid, semi-solid or liquid materials that can serve as vehicles, carriers or media for the active ingredient.
  • further auxiliaries are admixed in the manner known to the person skilled in the art.
  • the polymers and polyelectrolyte complexes are furthermore suitable as auxiliaries in pharmacy, preferably as or in coating compositions or binders for solid pharmaceutical forms. They can also be used in creams and as tablet coatings and tablet binders.
  • the agents according to the invention are a skin cleanser.
  • Preferred skin cleansers are soaps with a liquid to gel-like consistency, such as transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, paste-like soaps, soft soaps and washing pastes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and gels , Bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • a liquid to gel-like consistency such as transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, paste-like soaps, soft soaps and washing pastes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and gels , Bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • the agents according to the invention are cosmetic agents for the care and protection of the skin, nail care agents or preparations for decorative cosmetics.
  • Suitable skin cosmetic agents are e.g. B. face lotions, face masks, deodorants and other cosmetic lotions.
  • Agents for use in decorative cosmetics include, for example, concealers, theater paints, mascara and eye shadows, lipsticks, eyeliner pencils, eyeliners, blushers, powders and eyebrow pencils.
  • copolymers according to the invention can be used in nose strips for pore cleaning, in anti-acne agents, repellents, shaving agents, hair removal agents, intimate hygiene products, foot care products and in baby care.
  • the skin care products according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, care lotions and moisturizing lotions.
  • Skin cosmetic and dermatological agents based on the copolymers described above have advantageous effects.
  • the polymers can contribute, among other things, to moisturizing and conditioning the skin and to improving the feeling on the skin.
  • the polymers can also act as thickeners in the formulations. By adding the polymers according to the invention, a considerable improvement in skin tolerance can be achieved in certain formulations.
  • Skin cosmetic and dermatological agents preferably contain at least one copolymer in a proportion of approximately 0.001 to 30% by weight, preferably 0.01 to 20% by weight, very particularly preferably 0.1 to 12% by weight, based on the total weight of the agent.
  • light stabilizers based on the copolymers according to the invention have the property of increasing the residence time of the UV-absorbing ingredients in comparison to conventional auxiliaries such as polyvinylpyrrolidone.
  • the agents according to the invention can be used in a form suitable for skin care, such as. B. as a cream, foam, gel, stick, mousse, milk, spray (pump spray or spray containing blowing agent) or lotion.
  • the skin cosmetic preparations can also contain other active ingredients and auxiliaries customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaches, dyes, tinting agents, tanning agents, collagen, protein hydrolyzates, stabilizers, pH regulators, dyes , Salts, thickeners, gelling agents, consistency enhancers, silicones, humectants, refatting agents and other common additives.
  • active ingredients and auxiliaries customary in skin cosmetics as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaches, dyes, tinting agents, tanning agents, collagen, protein hydrolyz
  • Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as, for. B. paraffins, silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils, such as. B. sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as. B. triglycerides of C 6 -C 30 fatty acids, wax esters, such as. B. jojoba oil, fatty alcohols, petroleum jelly, hydrogenated lanolin and acetylated lanolin and mixtures thereof.
  • mineral and synthetic oils such as, for. B. paraffins, silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils, such as. B. sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as. B. triglycerides of C 6 -C
  • copolymers according to the invention can also be mixed with conventional polymers if special properties are to be set.
  • the skin cosmetic and dermatological preparations can also contain conditioning substances based on silicone compounds. gene included. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • the cosmetic or dermatological preparations are produced by customary methods known to the person skilled in the art.
  • the cosmetic and dermatological agents are preferably in the form of emulsions, in particular in the form of water-in-oil (W / O) or oil-in-water (O / W) emulsions.
  • W / O water-in-oil
  • O / W oil-in-water
  • Emulsions are prepared by known methods.
  • the emulsions generally contain conventional constituents, such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
  • conventional constituents such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
  • a suitable emulsion e.g. B. for a skin cream, etc.
  • a suitable emulsion generally contains an aqueous phase which is emulsified in an oil or fat phase by means of a suitable emulsifier system.
  • a copolymer according to the invention can be used to provide the aqueous phase.
  • Preferred fat components which can be contained in the fat phase of the emulsions are: hydrocarbon oils, such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophylum oil, lanolin and derivatives thereof, castor oil, seed oil, olive oil, jojoba oil, karite oil, hoplostethus oil; mineral oils whose distillation begins at atmospheric pressure at approx. 250 ° C and whose distillation end point is 410 ° C, e.g. B. Vaseline oil; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g. B.
  • the fat phase can also contain silicone oils soluble in other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • waxes can also be used, such as. B. Carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
  • an emulsion according to the invention can be present as an O / W emulsion.
  • Such an emulsion usually contains an oil phase, emulsifiers which stabilize the oil phase in the water phase and an aqueous phase which is usually present in a thickened state.
  • Preferred emulsifiers are O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides.
  • the agents according to the invention are a shower gel, a shampoo formulation or a bath preparation.
  • Such formulations contain at least one copolymer according to the invention and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants.
  • suitable active substances and / or auxiliary substances are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants as well as thickeners / gelling agents, skin conditioners and humectants.
  • formulations preferably contain 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, of surfactants, based on the total weight of the formulation.
  • All anionic, neutral, amphoteric or cationic surfactants commonly used in personal cleansing agents can be used in the washing, showering and bathing preparations.
  • Suitable anionic surfactants include for example alkyl sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulphosuccinates, N-Alkoylsarkosinate, acyl taurates, acyl isethionates, alkyl phosphates, Alkyletherphospha- te, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali metal and alkaline earth metal salts, eg. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.
  • These include e.g. B. sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzene sulfonate.
  • B sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzene sulfonate.
  • Suitable amphoteric surfactants are e.g. B. alkyl betaines, alkyiamidopropyl betaines, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, alkyl amphodiacetates or dipropionates.
  • alkyl betaines alkyiamidopropyl betaines
  • alkyl sulfobetaines alkyl glycinates
  • alkyl carboxyglycinates alkyl amphoacetates or propionates
  • alkyl amphoacetates or propionates alkyl amphodiacetates or dipropionates.
  • cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols with 6 to 20 carbon atoms in the alkyl chain, which can be linear or branched, with ethylene oxide and / or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
  • Alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • washing, showering and bathing preparations can contain conventional cationic surfactants, such as. B. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • shower gel / shampoo formulations thickeners such.
  • B table salt, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, other active ingredients and auxiliaries and water.
  • the agents according to the invention are a hair treatment agent.
  • Hair treatment compositions according to the invention preferably contain at least one copolymer according to the invention in an amount in the range from about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.
  • the hair treatment compositions according to the invention are preferably in the form of a foaming agent, hair mousse, hair gel, shampoos, hair sprays, hair foam, tip fluids, leveling agents for perms, hair dyeing and bleaching agents or "hot oil treatments".
  • the hair cosmetic preparations can be applied as (aerosol) spray, (aerosol) foam, gel, gel spray, cream, lotion or wax.
  • Hair sprays include both aerosol sprays and pump sprays without propellant.
  • Hair foams include both aerosol foams and pump foams without propellant.
  • Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components.
  • the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm.
  • the solids contents of these preparations are usually in a range from about 0.5 to 20% by weight.
  • These microdispersions generally do not require any emulsifiers or surfactants to stabilize them.
  • the hair cosmetic formulations according to the invention contain a) 0.05 to 20% by weight of at least one copolymer, as previously defined,
  • Alcohol is to be understood as all alcohols customary in cosmetics, e.g. B. ethanol, isopropanol, n-propanol.
  • compositions customary in cosmetics additives are to be understood, for example, blowing agents, defoamers, surface-active compounds, that is tensides t emulsifiers, foaming agents and solubilizers.
  • the surface-active compounds used can be anionic, cationic, amphoteric or neutral. Other common components can also be z. B.
  • preservatives perfume oils, opacifiers, active ingredients, UV filters, care substances such as panthenol, collagen, vitamins, protein hydrolyzates, alpha and beta hydroxycarboxylic acids, protein hydrolyzates, stabilizers, pH regulators, dyes, viscosity regulators, gelling agents, dyes, salts , Humectants, moisturizers, complexing agents and other common additives.
  • this includes all styling and conditioner polymers known in cosmetics, which can be used in combination with the polymers according to the invention if very special properties are to be set.
  • the preparations can also contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
  • copolymers according to the invention are particularly suitable as setting agents in hair styling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair foams (aerosol foams and pump foams without propellant gas).
  • spray preparations contain a) 0.1 to 10% by weight of at least one copolymer, as previously defined, b) 20 to 99.9% by weight of water and / or alcohol, c) 0 to 70% by weight .-% of at least one blowing agent, d) 0 to 20% by weight of further constituents.
  • Blowing agents are the blowing agents commonly used for hair sprays or aerosol foams. Mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide, nitrogen or compressed air are preferred.
  • a formulation according to the invention for aerosol hair foams contains
  • emulsifiers customarily used in hair foams can be used as emulsifiers.
  • Suitable emulsifiers can be nonionic, cationic or anionic or amphoteric.
  • nonionic emulsifiers are Laurethe, e.g. B. Laureth-4; Cetethe, e.g. B. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, e.g. B. Cetheareth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkyl polyglycosides.
  • cationic emulsifiers are cetyldimethyl-2-hydroxyethylammonium dihydrogen phosphate, cetyltrimonium chloride, cetyltrimmonium bromide, cocotrimonium methyl sulfate, quaternium-1 to x (INCI).
  • Anionic emulsifiers may for example be selected from the group of alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulphosuccinates, N-Alkoylsarkosinate, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali metal and alkaline earth metal salts, eg. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • a preparation suitable according to the invention for styling gels can be composed, for example, as follows:
  • gel formers can be advantageous in order to set special theological or other application properties of the gels.
  • All gel formers customary in cosmetics can be used as gel formers. These include slightly cross-linked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, e.g. B.
  • copolymers according to the invention can be used in cosmetic preparations as conditioning agents.
  • copolymers according to the invention can preferably be used in shampoo formulations as setting and / or conditioning agents.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoylsarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially alkali metal sulfonates, in particular the alkali metal sulfonates, especially alkali metal sulfonates, in particular the alkali metal sulfonates, in particular the alkali metal sulfonates, in particular the alkali metal sulfonates, in particular the alkali metal sulfonates, in particular the alkali metal sulfon
  • sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine deconyl sulfonate are suitable.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkylamphodiacetates or dipropionates.
  • cocodimethylsulfopropylbetaine laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols with 6 to 20 carbon atoms in the alkyl chain, which can be linear or branched, with ethylene oxide and / or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
  • Alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • the shampoo formulations can contain conventional cationic surfactants, such as. B. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • Conventional conditioning agents can be used in combination with the copolymers according to the invention in order to achieve certain effects in the shampoo formulations.
  • These include, for example, the aforementioned cationic polymers with the name Polyquaternium according to INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate , quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (Polyquatemium-4 and -10), acrylamide copolymers (Polyquatem
  • Protein hydrolyzates can also be used, and conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • silicone compounds for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • Other suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicone (CTFA).
  • Cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can also be used.
  • Another object of the invention is the use of a copolymer, as previously defined, as an auxiliary in pharmacy, preferably as or in coating compositions for solid pharmaceutical forms, for modifying rheological properties, as a surface-active compound, as or in adhesives (n ) as well as or in coating agent (s) for the textile, paper, printing and leather industries.
  • Feed 1 monomer mixture of:
  • Wako ® 50 [2,2'-azobis (2-aminopropane) dihydrochloride] 21 g water
  • TBA tert.-butyl acrylate TBMA: tert.-butyl methacrylate EMA: ethyl methacrylate MAM: methacrylamide NtBAM: N-tert.-butylacrylamide ACMO: acryloylmorpholine VP: vinylpyrrolidone DMAA: N, N-dimethylacrylamide AS: acrylic acid MAS: methacrylic acid NtBAEMA .-Butylaminoethyl methacrylate VI: vinylimidazole DMAPMAM: dimethylaminopropyl methacrylamide AMP: 2-amino-2-methylpropanol NG: degree of neutralization
  • VOC 80 aerosol hairspray (Examples No. 40 - 78)
  • Luvimer® 100P 1.0 (TBA / EA / MAS terpolymer, from BASF) water 15.5 dimethyl ether 40.0
  • VOC 55 aerosol hairspray (Examples No. 123 - 166)
  • Cremophor ® A 25 0.2 (Ceteareth 25, BASF)
  • preservatives soluble ethoxylated silicone, perfume.
  • Acrylic acid / Beheneth-25 methacrylate copolymers 50.0 (Aculyn® 28 from Rohm and Haas, 1% aqueous suspension) Production: The components of phases 1 and 2 are weighed in separately and homogenized. Phase 2 is slowly stirred into phase 1. A clear, viscous gel forms.
  • Phase 1 is weighed in separately and homogenized. Phase 1 is slowly stirred into phase 2. A clear, pourable gel is formed.
  • Cremophor A6 3.5 Ceteareth-6 (and) stearyl alcohol Cremophor A25 3.5 Ceteareth-25 glycerol monostearate s.e. 2.5 Glyceryl Stearate Paraffin Oil 7.5 Paraffin Oil Cetyl Alcohol 2.5 Cetyl Alcohol Luvitol EHO 3.2 Cetearyl Octanoate Vitamin-E-acetate 1, 0 Tocopheryl Acetate Nip-Nip 0.1 Methyl- and Propyl-4-hydroxybenzoate (7 : 3)

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Abstract

L'invention concerne des copolymères contenant du tert.-butyl(méth)acrylate, au moins un composé contenant, incorporés par polymérisation, des groupes amide, insaturés alpha , beta -éthyléniquement et de l'acide acrylique. L'invention concerne également des agents cosmétiques et pharmaceutiques contenant au moins un copolymère de ce type, ainsi que l'utilisation desdits copolymères.
PCT/EP2004/013984 2003-12-09 2004-12-08 Copolymeres a base de tert.-butyl(meth)acrylate et leur utilisation WO2005058989A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP04803650A EP1694728B1 (fr) 2003-12-09 2004-12-08 Copolymeres a base de tert.-butyl(meth)acrylate et leur utilisation dans laques a cheveux
US10/581,884 US7858076B2 (en) 2003-12-09 2004-12-08 Copolymers based on tert-butyl(meth) acrylate and use thereof
JP2006543468A JP2007514031A (ja) 2003-12-09 2004-12-08 ｔｅｒｔ−ブチル（メタ）アクリレートをベースとするコポリマーおよびその使用
CA002547754A CA2547754A1 (fr) 2003-12-09 2004-12-08 Copolymeres a base de tert.-butyl(meth)acrylate et leur utilisation
DE502004007861T DE502004007861D1 (de) 2003-12-09 2004-12-08 Copolymere auf basis von tert.-butyl(meth)acrylat und deren verwendung in haarsprays

Applications Claiming Priority (2)

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DE10357486 2003-12-09
DE10357486.7 2003-12-09

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WO2005058989A1 true WO2005058989A1 (fr) 2005-06-30

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KR (1) KR20060127406A (fr)
CN (1) CN1890278A (fr)
AT (1) ATE404250T1 (fr)
CA (1) CA2547754A1 (fr)
DE (1) DE502004007861D1 (fr)
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Cited By (2)

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CN103254857B (zh) * 2013-05-11 2015-04-29 北京化工大学 一种醇溶性自交联型丙烯酸树脂胶黏剂及其制备方法

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US7858076B2 (en) 2010-12-28
KR20060127406A (ko) 2006-12-12
EP1694728B1 (fr) 2008-08-13
CA2547754A1 (fr) 2005-06-30
ATE404250T1 (de) 2008-08-15
DE502004007861D1 (de) 2008-09-25
CN1890278A (zh) 2007-01-03
US20070116660A1 (en) 2007-05-24
ES2310764T3 (es) 2009-01-16

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